WO1992014851A1 - Procede de production de titane metallique et d'intermediaires utiles dans le traitement d'ilmenite et de mineraux associes - Google Patents
Procede de production de titane metallique et d'intermediaires utiles dans le traitement d'ilmenite et de mineraux associes Download PDFInfo
- Publication number
- WO1992014851A1 WO1992014851A1 PCT/AU1992/000062 AU9200062W WO9214851A1 WO 1992014851 A1 WO1992014851 A1 WO 1992014851A1 AU 9200062 W AU9200062 W AU 9200062W WO 9214851 A1 WO9214851 A1 WO 9214851A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fluoride
- ammonium
- alkali
- titanium
- hexafluorotitanate
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/002—Compounds containing, besides titanium, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/006—Compounds containing, besides zirconium, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1204—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1263—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction
- C22B34/1268—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using alkali or alkaline-earth metals or amalgams
- C22B34/1272—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using alkali or alkaline-earth metals or amalgams reduction of titanium halides, e.g. Kroll process
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1263—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction
- C22B34/1277—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using other metals, e.g. Al, Si, Mn
Definitions
- This invention relates to a process for the production of metallic titanium and intermediates useful in the processing of ilmenite and related minerals.
- Australia is the major world producer of ilmenite which is exported for about A$75 per tonne.
- the cost of metallic titanium in ingot form is about A$20,000 per tonne.
- the value of metallic titanium is very much greater.
- Metallic titanium is, by comparison with most other metals and alloys, very resistant to chemical corrosion and is in great demand in the manufacture of chemical plants and for heat- exchangers and other units in power plants.
- Another important application is the use of metallic titanium in surgical and dental implants and supports. On a strength-for-weight basis, metallic titanium is stronger than steel and is widely used in the construction of supersonic military aircraft.
- a process for the production of metallic titanium characterized in that the process comprises reducing a titanium-fluorine compound selected from titanium tetrafluoride and any hexafluorotitanate soluble in a molten fluoroaluminate, with metallic aluminium in a molten fluoroaluminate.
- the preferred titanium-fluorine compound is an alkali hexafluorotitanate, more preferably, sodium hexafluorotitanate (Na2TiFg) or potassium hexafluorotitanate (J ⁇ TiFg).
- the molten fluoroaluminate is a hexafluoroaluminate, more preferably, cryolite (Na3AlFg).
- cryolite Na3AlFg
- sodium hexafluorotitanate (Na2TiFg) or potassium hexafluorotitanate K ⁇ ⁇ F ) is dissolved in cryolite (Na 3 AlF 6 ) at about 1000 to 1100° C and metallic aluminium (Al) is added.
- Aluminium is chosen as the reductant because it is compatible with the melt, being oxidized in the first instance to aluminium fluoride (AIF3) and then interacting with sodium fluoride (NaF) to form cryolite (Na AlFg).
- aluminium is much less energy-intensive and cheaper to produce than sodium or magnesium reductants used in the current processes.
- Metallic titanium is achieved as a consequence of the relative densities of the reactants and the molten medium. Aluminium is less dense than cryolite which, in turn, is less dense than metallic titanium. Therefore, metallic titanium has a tendency to collect at the bottom of the reaction bath and may be tapped from that position with molten cryolite.
- the pure compound Na3AlFg constitutes a neutral molten medium. If the melt is deficient in NaF, i.e. contains an excess of AIF3, the medium is acidic. If the melt contains an excess of NaF, then the medium is basic.
- Na2TiFg may be reduced by aluminium to metallic titanium directly in acidic or basic cryolite i.e. the direct reduction from Ti(IV) to Ti(0) may occur.
- the ultimate reduction to the metal is preferably carried out in neutral cryolite. Under neutral conditions Ti(IV) needs to be reduced only to Ti(II), which will disproportionate spontaneously in neutral medium according to the following equation:
- Ti(0) Metallic titanium i.e. Ti(0) is produced, and the Ti(IV) regenerated by the disproportionation reaction is available for reduction by aluminium to Ti(II) and subsequent disproportionation. This cyclic process continues until all Ti(IV) is reduced to Ti(0).
- Na2TiFg is added progressively to the cryolite bath in order to minimise loss of volatile ⁇ F4 which might result from thermal decomposition of Na2TiFg.
- Sodium fluoride (NaF) may be added with Na2TiFg preferably in the ratio 2:1 in order to maintain neutrality of the molten cryolite in accordance with the above equation.
- Aluminium may be added in a stoichiometric amount or in excess.
- the process of the present invention may form the basis of a continuous process similar to that used for aluminium smelting.
- Na2TiFg, Al and NaF may be added to the cryolite medium, in which case the product of the reaction is cryolite itself.
- a mixture of molten cryolite and the suspended metal may then be tapped from the bottom of the reactor.
- the solid material produced may then be crushed and initial separation of cryolite and titanium metal carried out by any suitable known technique, for example, flotation or cyclone separation.
- Any cryolite remaining attached to the titanium metal particles may be dissolved away from the titanium metal using any solution based on a metal cation which will complex with fluoride ions, preferably a solution of a water soluble aluminium compound, such as a solution of aluminium nitrate.
- a metal cation which will complex with fluoride ions
- a water soluble aluminium compound such as a solution of aluminium nitrate.
- an alternative procedure of electrowinning may be used in which Na2TiFg and AIF3 are added continuously to a cryolite bath, Ti being deposited at a graphite cathode.
- a sacrificial anode reaction could be utilized.
- AIF3 would need to be added in the correct stoichiometric amount relative to N 2TiFg (4:3) in order to maintain neutrality in the cryolite.
- the feedstock for the process of the present invention is preferably K j TiFg or Na2TiFg. It will be understood however that other sources of titanium may be used, such as, ⁇ F4.
- ⁇ F4 A major disadvantage of ⁇ F4 is that it reacts readily with atmospheric moisture to form hydrogen fluoride and is difficult and dangerous to handle, whereas Na2TiFg and I ⁇ TiFg are stable in moist air and safe and easy to handle.
- step b) adding an ammonium fluoride to the metal fluoride compound dissolved in the organic solvent in step a) to precipitate an ammonium fluorometallate from the organic solvent; and c) dissolving the ammonium fluorometallate from step b) in water and adding an alkali fluoride to produce an alkali fluorometallate and an ammonium fluoride.
- the related minerals may include, for example, other titaniferous ores such as rutile, titaniferous slags or zircon.
- the organic solvent from step b) may be optionally recycled to step a) and the ammonium fluoride from step c) may be optionally recycled to step b).
- the metal fluoride compound in step a) is selected from titanium tetrafluoride, zirconium tetrafluoride and tin tetrafluoride.
- the metal fluoride compound in step a) is often contaminated with an impurity such as a metal oxidefluoride, for example, titanium oxidefluoride.
- an impurity such as a metal oxidefluoride, for example, titanium oxidefluoride.
- titanium oxidefluoride is insoluble in organic solvents, this impurity can be separated from the titanium fluoride compound by dissolving the mixture in an organic solvent.
- the metal oxidefluoride impurity remaining as a residue after treatment with the organic solvent can be heated to produce the desired metal fluoride compound and a metal oxide.
- the metal oxide may then be treated to produce a metal oxide pigment or a refractory ceramic or recycled to produce metal fluoride compounds such as ⁇ F4 or ZrF4-
- the organic solvent in step a) is preferably an alcohol, such as, for example, methanol or ethanol.
- ammonium fluoride in step b) is selected from ammonium fluoride (NH4F) or ammonium bifluoride (NH4HF2).
- the ammonium fluorometallate produced in step b) may be ammonium fluorotitanate, such as, for example, ammonium hexafluorotitanate ((NH4 ⁇ TiFg or ammonium fluorozirconate, such as, for example, ammonium heptafluorozirconate ((NH4)3 Zr F7) and ammonium hexafluorozirconate ZrFg).
- the ammonium fluorometallate is ammonium hexafluorotitanate ((N ⁇ TiFg) which may be used to produce K ⁇ TiFg or Na2TiFg which is the preferred feedstock employed in the process for the production of metallic titanium described above.
- the alkali fluoride in step c) is potassium fluoride (KF) or sodium fluoride (NaF).
- the alkali fluorometallate produced in step c) may be l ⁇ TiF ⁇ or Na2TiFg which is the preferred feedstock employed in the process for the production of metallic titanium described above.
- step a) water and optionally base is added to the metal fluoride compound dissolved in the organic solvent in step a) to produce a hydrated metal oxide.
- the hydrated metal oxide product from the alternative process may be treated to produce a metal oxide pigment or a refractory ceramic.
- the ammonium fluorometallate from step b) is pyrohydrolysed to produce a hydrated metal oxide, an ammonium fluoride and hydrogen fluoride.
- the ammonium fluoride may be optionally recycled to step b).
- the hydrogen fluoride may be optionally treated with silicon dioxide and an alkali fluoride to produce an alkali fluorosilicate.
- the alkali fluorosilicate may then be heated to produce silicon tetrafluoride and an alkali fluoride.
- the silicon tetrafluoride may be optionally recycled for use in the process for the formation of ⁇ F4 from minerals such as ilmenite and the subsequent conversion of T1F4 to ⁇ O2 as described in our co-pending Australian Patent Application No. 48186/90.
- the further alternative process may be performed using any suitable pyrohydrolysis technique.
- a flow system having air with entrained water vapour may be streamed over a bed of the ammonium fluorometallate at temperatures sufficiently low to prevent sublimation of, for example, ⁇ F4 from a fluorotitanate (200-300 °C) or ZrF4 from a fluorozirconate (450-500 °C).
- the residues are hydrated ⁇ O2 or ZrO ⁇ Volatile HF and NH4F are carried out of the reaction zone in the air stream and may be condensed to form solid NH4F and an aqueous solution of HF.
- the solid NH4F may be optionally recycled to step b).
- the HF may be treated with Si ⁇ 2 and KF or NaF to form -E ⁇ SiFg or Na2SiFg which may be recovered and heated to about 600 to 700 ⁇ C to yield SiF4 which is recycled to a mineral reactor bed to produce further T1F4 and ZrF4 as disclosed in Australian Patent Application No. 48186/90.
- the KF or NaF residues may be recycled to step c). 100% recovery of ⁇ O2 or Z >2 and all of the fluoride in the compounds volatilized during pyrohyrolysis has been demonstrated experimentally for pyrohydrolysis of and under such conditions.
- the T >2 and Zr ⁇ 2 produced by the pyrohydrolysis in the further alternative process are hydrated and therefore more chemically reactive than the T ⁇ O2 and Zr ⁇ 2 obtained from conventional processes.
- conventional processing of ilmenite and related minerals such as zircon high-temperature oxidation or hydrolysis reactions are used to convert intermediates into titanium dioxide ( ⁇ O2) or zirconium dioxide (Zr ⁇ 2).
- titanium tetrachloride (TiC-4) is burned in oxygen above 1000 °C to produce Ti ⁇ 2-
- zircon is fused with alkaline materials at about 1000 °C and then leached with aqueous solution. Sometimes the zircon is pre-heated by plasma techniques to about 2000 °C before leaching.
- the ⁇ O2 and Zr ⁇ 2 products obtained in these conventional processes are refractory not particularly amenable to subsequent purification or other processing.
- a process for the production of an intermediate useful in the processing of ilmenite and related minerals characterized in that the process comprises producing an aqueous solution of a titanium or zirconium compound soluble in water or capable of reacting with water and adding an alkali fluoride and optionally excess fluoride to the aqueous solution to produce an alkali fluorotitanate or an alkali fluorozirconate.
- the source of excess fluoride may be hydrogen fluoride or alkali fluoride.
- the titanium compound capable of reacting with water in the further alternative process is preferably ⁇ CI4 which is produced in the chloride pigment process described above.
- the titanium compound soluble in water in the further alternative process is ⁇ OSO4 which is the intermediate produced in the sulphate pigment process. Both of these compounds may be used to produce ⁇ TiFg or Na2TiFg which is the preferred feedstock employed in the process for the production of metallic titanium described above.
- An example of zirconium compound capable of reacting with water is ZrCl .
- a mixture of about 30g Na3AlFg and 1.9g of ⁇ TiFg was melted at 1090 °C in a graphite crucible with a loose-fitting graphite lid.
- the inert gas argon was bubbled through a graphite lance dipping into the melt.
- a total of 0.28g of Al and 0.67g of NaF was added during the reaction by introducing several small compressed pellets of Al and NaF through the lance. After a period of settling, the melt was returned to room temperature and the graphite crucible was sectioned. A black powder was found to have settled towards the bottom of the solidified melt.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
L'invention concerne un procédé de production de titane métallique, qui se caractérise par le fait qu'il consiste à réduire un composé de titane-fluor choisi parmi un tétrafluorure de titane et tout hexafluorotitanate soluble dans un fluoroaluminate fondu. On décrit également un procédé de production d'intermédiaires qui sont utiles dans le traitement d'ilménite et de minéraux associés.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP50479192A JPH06505306A (ja) | 1991-02-21 | 1992-02-21 | 金属チタンならびにチタン鉄鉱および関連鉱物を処理する際に有用な中間体の製造方法 |
US08/107,787 US5397375A (en) | 1991-02-21 | 1992-02-21 | Process for the production of metallic titanium and intermediates useful in the processing of ilmenite and related minerals |
AU12741/92A AU650724B2 (en) | 1991-02-21 | 1992-02-21 | Process for the production of metallic titanium |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AUPK472191 | 1991-02-21 | ||
AUPK4721 | 1991-02-21 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1992014851A1 true WO1992014851A1 (fr) | 1992-09-03 |
Family
ID=3775240
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/AU1992/000062 WO1992014851A1 (fr) | 1991-02-21 | 1992-02-21 | Procede de production de titane metallique et d'intermediaires utiles dans le traitement d'ilmenite et de mineraux associes |
Country Status (4)
Country | Link |
---|---|
US (2) | US5397375A (fr) |
JP (1) | JPH06505306A (fr) |
AU (1) | AU650724B2 (fr) |
WO (1) | WO1992014851A1 (fr) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005002766A1 (fr) * | 2003-07-04 | 2005-01-13 | Commonwealth Scientific And Industrial Research Organisation | Procede et dispositif permettant la production de composes metalliques |
AU2004253193B2 (en) * | 2003-07-04 | 2006-12-21 | Commonwealth Scientific And Industrial Research Organisation | A method and apparatus for the production of metal compounds |
WO2007109847A1 (fr) * | 2006-03-27 | 2007-10-04 | Commonwealth Scientific And Industrial Research Organisation | Appareil et procedes de production de composes metalliques |
EP2617842A1 (fr) * | 2012-01-18 | 2013-07-24 | Shenzhen Sunxing Light Alloys Materials Co., Ltd | Procédé de fabrication du titane spongieux |
EP2617844A1 (fr) * | 2012-01-18 | 2013-07-24 | Shenzhen Sunxing Light Alloys Materials Co., Ltd | Procédé technologique de préparation de titane spongieux à partir de matières premières de fluotitanate de sodium |
EP2631310A1 (fr) * | 2012-02-22 | 2013-08-28 | Shenzhen Sunxing Light Alloys Materials Co., Ltd | Procédé permettant de préparer cycliquement une éponge en titane et de coproduire du cryolite de potassium à l'aide de fluotitanate de potassium comme matériau intermédiaire |
EP2631309A1 (fr) * | 2012-02-22 | 2013-08-28 | Shenzhen Sunxing Light Alloys Materials Co., Ltd | Procédé permettant de préparer une éponge en titane et de coproduire du cryolite de sodium à l'aide de fluotitanate de sodium comme matériau intermédiaire |
US8632724B2 (en) | 2008-04-21 | 2014-01-21 | Commonwealth Sci. and Ind. Res. Org. | Method and apparatus for forming titanium-aluminium based alloys |
US8834601B2 (en) | 2009-12-18 | 2014-09-16 | Commonwealth Scientific And Industrial Research Organisation | Method for producing low aluminium titanium-aluminium alloys |
Families Citing this family (22)
Publication number | Priority date | Publication date | Assignee | Title |
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US5788948A (en) * | 1993-10-22 | 1998-08-04 | The University Of Melbourne | Process for the production of fluorometallate salts useful in the processing of mineral sands and related materials |
US6440383B1 (en) | 1999-06-24 | 2002-08-27 | Altair Nanomaterials Inc. | Processing aqueous titanium chloride solutions to ultrafine titanium dioxide |
US6375923B1 (en) | 1999-06-24 | 2002-04-23 | Altair Nanomaterials Inc. | Processing titaniferous ore to titanium dioxide pigment |
US6548039B1 (en) | 1999-06-24 | 2003-04-15 | Altair Nanomaterials Inc. | Processing aqueous titanium solutions to titanium dioxide pigment |
US6153164A (en) * | 1999-10-04 | 2000-11-28 | Starmet Corporation | Method for producing uranium oxide from uranium tetrafluoride and a phyllosilicate mineral |
AU2005271781A1 (en) * | 2004-07-13 | 2006-02-16 | Altairnano, Inc. | Ceramic structures for prevention of drug diversion |
EP1683762A1 (fr) * | 2005-01-24 | 2006-07-26 | BRETON s.p.a. | Procédé de préparation d'oxyde de titane utilisant une solution aqueuse de fluoride d'ammonium |
ATE531827T1 (de) * | 2005-01-27 | 2011-11-15 | Peruke Proprietary Ltd | Verfahren zur herstellung des titanpulvers |
AU2006283170A1 (en) * | 2005-08-23 | 2007-03-01 | Altairnano, Inc. | Highly photocatalytic phosphorus-doped anatase-TiO2 composition and related manufacturing methods |
US20080038482A1 (en) * | 2006-03-02 | 2008-02-14 | Fred Ratel | Method for Low Temperature Production of Nano-Structured Iron Oxide Coatings |
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WO2007103824A1 (fr) * | 2006-03-02 | 2007-09-13 | Altairnano, Inc. | Oxydes métalliques nanostructurés |
US20080254258A1 (en) * | 2007-04-12 | 2008-10-16 | Altairnano, Inc. | Teflon® replacements and related production methods |
NZ586672A (en) * | 2008-01-14 | 2011-06-30 | Peruke Proprietary Ltd | The production of titanium trifluoride |
US8007562B2 (en) * | 2008-12-29 | 2011-08-30 | Adma Products, Inc. | Semi-continuous magnesium-hydrogen reduction process for manufacturing of hydrogenated, purified titanium powder |
KR101523978B1 (ko) * | 2009-09-11 | 2015-05-29 | 더 사우스 아프리칸 뉴클리어 에너지 코퍼레이션 리미티드 | 미네랄의 처리 |
MY167700A (en) * | 2011-04-08 | 2018-09-21 | Shinetsu Chemical Co | Preparation of complex fluoride and complex fluoride phosphor |
EP3561091A1 (fr) | 2011-12-22 | 2019-10-30 | Universal Achemetal Titanium, LLC | Procédé pour l'extraction et le raffinage du titane |
CN104911376B (zh) * | 2015-07-17 | 2017-01-04 | 东北大学 | 两段铝热还原制取钛或钛铝合金并副产无钛冰晶石的方法 |
CN109996896B (zh) | 2016-09-14 | 2021-10-26 | 通用金属钛有限责任公司 | 生产钛-铝-钒合金的方法 |
CA3049769C (fr) | 2017-01-13 | 2023-11-21 | Universal Achemetal Titanium, Llc | Alliage-mere de titane pour alliages a base de titane-aluminium |
CN113463135B (zh) * | 2021-07-30 | 2022-09-30 | 昆明理工大学 | 一种氟化物熔盐中二氧化钛溶解-电解制备金属钛的方法 |
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1992
- 1992-02-21 US US08/107,787 patent/US5397375A/en not_active Expired - Fee Related
- 1992-02-21 AU AU12741/92A patent/AU650724B2/en not_active Ceased
- 1992-02-21 JP JP50479192A patent/JPH06505306A/ja active Pending
- 1992-02-21 WO PCT/AU1992/000062 patent/WO1992014851A1/fr active Application Filing
-
1995
- 1995-01-23 US US08/377,103 patent/US5482691A/en not_active Expired - Fee Related
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SU181638A1 (fr) * | уральский научно исследовательский химический институт | |||
DE407508C (de) * | 1920-12-21 | 1924-12-16 | Westinghouse Lamp Co | Herstellung von seltenen und von sehr hoch schmelzenden Metallen |
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Also Published As
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US5397375A (en) | 1995-03-14 |
JPH06505306A (ja) | 1994-06-16 |
US5482691A (en) | 1996-01-09 |
AU1274192A (en) | 1992-09-15 |
AU650724B2 (en) | 1994-06-30 |
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